Rovibrational Energies of 13C16O2 Determined with Kilohertz Accuracy.

Accurate spectroscopic data of carbon dioxide are widely used in many important applications, such as carbon monitoring missions. Here, we present comb-locked cavity ring-down saturation spectroscopy of the second most abundant isotopologue of CO2, 13C16O2. We determined the positions of 88 lines in three vibrational bands in the 1.6 µm region, 30011e/30012e/30013e-00001e, with an accuracy of a few kHz. Based on the analysis of combination differences, we obtained for the first time the ground-state rotational energies with kHz accuracy. We also provide a set of hybrid line positions for 150 13C16O2 transitions. The rotational energies (J < 50) in the 30013e vibrational state can be fitted by a set of rotational and centrifugal constants with deviations within a few kHz, indicating that the 30013e state is free of perturbations. These precise isotopic line positions will be utilized to improve the Hamiltonian model and quantitative remote sensing of carbon dioxide. Moreover, they will help to track changes in the carbon source and sink through isotopic analysis.

Mid-infrared-near-infrared double-resonance spectroscopy of molecules with kilohertz accuracy.

Precision measurements of molecular transitions to highly excited states are needed in potential energy surface modeling, state-resolved chemical dynamics studies, and astrophysical spectra analysis. Selective pumping and probing of molecules are often challenging due to the high state density and weak transition moments. We present a mid-infrared and near-infrared double-resonance spectroscopy method for precision measurements. As a demonstration, Doppler-free stepwise two-photon absorption spectra of 13CO2 were recorded by pumping the fundamental transition of R14 (00011)-(00001) and probing the P15 (00041)-(00011) transition enhanced by a high-finesse optical cavity, and the transition frequencies were determined with an accuracy of a few kilohertz.

Precision spectroscopy of molecular hydrogen.

Precision measurements on the hydrogen molecule are of fundamental importance in understanding molecular theory. Comparison of accurate experimental data and theoretical results are used to test the quantum electrodynamics theory and determine physical constants used in the calculation. We review recent advances and perspectives in the precision spectroscopy of molecular hydrogen, representing state-of-the-art molecular spectroscopy methods and cutting-edge high-precision calculations.

Multiple Gas Detection by Cavity-Enhanced Raman Spectroscopy with Sub-ppm Sensitivity.

Accurate and sensitive detection of multicomponent trace gases below the parts-per-million (ppm) level is needed in a variety of medical, industrial, and environmental applications. Raman spectroscopy can identify multiple molecules in the sample simultaneously and has excellent potential for fast diagnosis of various samples, but applications are often limited by its sensitivity. In this contribution, we report the development of a cavity-enhanced Raman spectroscopy instrument using a narrow-line width 532 nm laser locked with a high-finesse cavity through a Pound-Drever-Hall locking servo, which allows continuous measurement in a broad spectral range. An intracavity laser power of up to 1 kW was achieved with an incident laser power of about 240 mW, resulting in a significant enhancement of the Raman signal in the range of 200-5000 cm-1 and a sub-ppm sensitivity for various molecules. The technique is applied in the detection of different samples, including ambient air, natural gas, and reference gas of sulfur hexafluoride, demonstrating its capability for the quantitative measurement of various trace components.

kHz-precision wavemeter based on reconfigurable microsoliton.

The mode-locked microcomb offers a unique and compact solution for photonics applications, ranging from the optical communications, the optical clock, optical ranging, the precision spectroscopy, novel quantum light source, to photonic artificial intelligence. However, the photonic micro-structures are suffering from the perturbations arising from environment thermal noises and also laser-induced nonlinear effects, leading to the frequency instability of the generated comb. Here, a universal mechanism for fully stabilizing the microcomb is proposed and experimentally verified. By incorporating two global tuning approaches and the autonomous thermal locking mechanism, the pump laser frequency and repetition rate of the microcomb can be controlled independently in real-time without interrupting the microcomb generation. The high stability and controllability of the microcomb frequency enables its application in wavelength measurement with a precision of about 1 kHz. The approach for the full control of comb frequency could be applied in various microcomb platforms, and improve their performances in timing, spectroscopy, and sensing.

Fast atom-trap analysis of 39Ar with isotope pre-enrichment.

We demonstrate fast analysis of 39Ar/Ar at the 10-16 level using a mass spectrometer for isotope pre-enrichment and an atom trap for counting. An argon gas sample first passes through a dipole mass separator that reduces the dominant isotope 40Ar by two orders of magnitude while preserving both the rare tracer isotope 39Ar and a minor stable isotope 38Ar for control purposes. Measurements of both natural and enriched samples with atom trap trace analysis demonstrate that the 39Ar/38Ar ratios change less than 10%, while the overall count rates of 39Ar are increased by one order of magnitude. By overcoming the analysis-speed bottleneck, this advance will benefit large-scale applications of 39Ar dating in the earth sciences, particularly for mapping ocean circulation.

An atom trap system for 39Ar dating with improved precision.

Cosmogenic 39Ar dating is an emerging technique in dating mountain glacier ice, mapping ocean circulation, and tracing groundwater flow. We have realized an atom-trap system for the analysis of the radioactive isotope 39Ar (half-life = 269 years) in environmental samples. The system is capable of analyzing small (1-5 kg) environmental water or ice samples and achieves a count rate of 10 atoms/h for 39Ar at the modern isotopic abundance level of 8 × 10-16. By switching frequently between counting 39Ar atoms and measuring the stable and abundant isotope 38Ar, drift effects in the trapping efficiency are largely suppressed, leading to a more precise measurement of the isotope ratio 39Ar/38Ar. Moreover, cleaning techniques are developed to alleviate cross-sample contamination, reducing the background 39Ar count rate down to <0.5 atoms/h. These advances allow us to determine the 39Ar age in the range of 250-1300 years with precisions of <20%.

Monitoring atmospheric 85Kr by atom counting.

Radioactive 85Kr is a major gaseous fission product emitted into the air by the nuclear fuel reprocessing industry. Measuring atmospheric 85Kr has applications in environmental monitoring, atmospheric transport model validation and dating of environmental water samples, including groundwater, sea water and glacier ice. We present an ultra-sensitive method for fast analysis of atmospheric 85Kr at 10-5 parts per trillion level. This method is based on laser cooling and trapping and is capable of counting individual 85Kr atoms. Measurements at the 3% precision level can be made on krypton extracted from 1L STP of air with a turnaround time of 1.5 h. Moreover, we have realized a system for continuous air sampling over days to weeks. Based on this atom-counting technology and a portable air sample integrator we have realized atmospheric 85Kr baseline monitoring in Hefei, China, for over 20 months. The technological advances presented in this work lay the ground for a global atmospheric 85Kr monitoring network.

Optical-Optical Double-Resonance Absorption Spectroscopy of Molecules with Kilohertz Accuracy.

Selective pumping and probing of highly excited states of molecules are essential in various studies but are also challenging because of high density of states, weak transition moments, and lack of precise spectroscopy data. We develop a comb-locked cavity-assisted double-resonance spectroscopy (COCA-DR) method for precision measurements using low-power continuous-wave lasers. A high-finesse cavity locked with an optical frequency comb is used to enhance both the pumping power and the probing sensitivity. As a demonstration, Doppler-free stepwise two-photon absorption spectra of CO2 were recorded by using two milliwatt diode lasers (1.60 and 1.67 µm), and the rotation energies in a highly excited state (CO-stretching quanta = 8) were determined with an unprecedented accuracy of a few kilohertz.

A well-isolated vibrational state of CO2 verified by near-infrared saturated spectroscopy with kHz accuracy.

Quantitative determination of atmospheric CO2 concentration by remote sensing relies on accurate line parameters. Lamb dips of the lines up to J'' = 72 in the 30013-00001 band at 1605 nm were measured using a comb-locked cavity ring-down spectrometer, and the positions were determined with an accuracy of a few kHz. A simple effective Hamiltonian model can fit the rotational energies in the 30013 state ideally within the experimental accuracy, indicating that the vibrational state is well-isolated and can be regarded as free from perturbations. From a comparison between other bands using a similar analysis, we conclude that the transitions in the 30013-00001 band could be more suitable as reference lines for sensing applications with the potentially improved line parameter accuracy.

Precision spectroscopy of atomic helium.

Helium is a prototype three-body system and has long been a model system for developing quantum mechanics theory and computational methods. The fine-structure splitting in the 23P state of helium is considered to be the most suitable for determining the fine-structure constant α in atoms. After more than 50 years of efforts by many theorists and experimentalists, we are now working toward a determination of α with an accuracy of a few parts per billion, which can be compared to the results obtained by entirely different methods to verify the self-consistency of quantum electrodynamics. Moreover, the precision spectroscopy of helium allows determination of the nuclear charge radius, and it is expected to help resolve the 'proton radius puzzle'. In this review, we introduce the latest developments in the precision spectroscopy of the helium atom, especially the discrepancies among theoretical and experimental results, and give an outlook on future progress.

Dual Separation of Krypton and Argon from Environmental Samples for Radioisotope Dating.

The noble gas radioisotopes 85Kr, 81Kr, and 39Ar are nearly ideal environmental tracers because of their chemical inertness and simple transport mechanisms. Recent advances in Atom Trap Trace Analysis have enabled measurements of 85Kr and 81Kr using 10-20 kg of water or ice, and 39Ar in only a few kilograms, making these tracers available to be applied in the earth sciences on a large-scale. To meet the resulting increase in demand, we have developed an automated process for the dual separation of krypton and argon from environmental samples based on titanium gettering and gas chromatography. 0.5-4 L STP air samples have been purified, demonstrating purities and recoveries of >90% for krypton and >99% for argon within 90-120 min of processing time. Samples of high methane admixtures, a challenge regularly encountered in groundwater applications, have been purified by exploiting the full potential of titanium gettering at high temperatures (>1000 °C). Samples with 0.4-48 L STP of methane admixture are processed in 2-5 h without compromising purity or recovery. The applicability of the purification system is further demonstrated using actual groundwater samples with carbon dioxide and methane content in the extracted gas up to 16 L STP and 42 L STP, respectively.

Communication: Molecular near-infrared transitions determined with sub-kHz accuracy.

Precise molecular transition frequencies are needed in various studies including the test of fundamental physics. Two well isolated ro-vibrational transitions of 12C16O at 1.57 µm, R(9) and R(10) in the second overtone band, were measured by a comb-locked cavity ring-down spectrometer. Despite the weakness of the lines (Einstein coefficient A≃0.008 s-1), Lamb-dip spectra were recorded with a signal-to-noise ratio over 1000, and the line positions were determined to be 191 360 212 761.1 and 191 440 612 662.2 kHz, respectively, with an uncertainty of 0.5 kHz (δν/ν=2.6×10-12). The present work demonstrates the possibility to explore extensive molecular lines in the near-infrared with sub-kHz accuracy.

Identification of alcohol conformers by Raman spectra in the C-H stretching region.

The spontaneous polarized Raman spectra of normal and deuterated alcohols (C2-C5) have been recorded in the C-H stretching region. In the isotropic Raman spectra, a doublet of -CαH stretching vibration is found for all alcohols at below 2900 cm(-1) and above 2950 cm(-1). By comparing the experimental and calculated spectra of various deuterated alcohols, the doublets are attributed to the -CαH stretching vibration of different conformers. For ethanol, the band observed at 2970 cm(-1) is assigned as the stretching vibration of -CαH in the Cα-O-H plane of the gauche-conformer, while the band at 2895 cm(-1) is contributed from both the -CαH2 symmetrical stretching vibration of the trans-conformer and the -CαH stretching vibration out of the Cα-O-H plane of the gauche-conformer. The population of gauche-conformer is estimated to be 54% in liquid ethanol. For the larger alcohols, the same assignments for the doublet are obtained, and the populations of gauche-conformers with plane carbon skeleton are found to be slightly larger than that of ethanol, which is consistent with results from molecular dynamics simulations.

Ultrasensitive, self-calibrated cavity ring-down spectrometer for quantitative trace gas analysis.

A cavity ring-down spectrometer is built for trace gas detection using telecom distributed feedback (DFB) diode lasers. The longitudinal modes of the ring-down cavity are used as frequency markers without active-locking either the laser or the high-finesse cavity. A control scheme is applied to scan the DFB laser frequency, matching the cavity modes one by one in sequence and resulting in a correct index at each recorded spectral data point, which allows us to calibrate the spectrum with a relative frequency precision of 0.06 MHz. Besides the frequency precision of the spectrometer, a sensitivity (noise-equivalent absorption) of 4×10-11 cm-1 Hz-1/2 has also been demonstrated. A minimum detectable absorption coefficient of 5×10-12 cm-1 has been obtained by averaging about 100 spectra recorded in 2  h. The quantitative accuracy is tested by measuring the CO2 concentrations in N2 samples prepared by the gravimetric method, and the relative deviation is less than 0.3%. The trace detection capability is demonstrated by detecting CO2 of ppbv-level concentrations in a high-purity nitrogen gas sample. Simple structure, high sensitivity, and good accuracy make the instrument very suitable for quantitative trace gas analysis.

Analysis of krypton-85 and krypton-81 in a few liters of air.

Long-lived radioactive krypton isotopes, (81)Kr (t1/2 = 229,000 year) and (85)Kr (t1/2 = 10.76 year), are ideal tracers. (81)Kr is cosmogenic and can be used for dating groundwater beyond the (14)C age. (85)Kr is a fission product and can be applied in atmospheric studies, nuclear safety inspections, and dating young groundwater. It has long been a challenge to analyze radio-krypton in small samples, in which the total number of such isotopes can be as low as 1 × 10(5). This work presents a system developed to analyze (81)Kr and (85)Kr from a few liters of air samples. A separation system based on cryogenic distillation and gas chromatographic separation is used to extract krypton gas with an efficiency of over 90% from air samples of 1-50 L. (85)Kr/Kr and (81)Kr/Kr ratios in krypton gases are determined from single-atom counting using a laser-based atom trap. In order to test the performance of the system, we have analyzed various samples collected from ambient air and extracted from groundwater, with a minimum size of 1 L. The system can be applied to analyze (81)Kr and (85)Kr in environmental samples including air, groundwater, and ices.

[A very sensitive CW cavity ring-down spectrometer and its application].

A cavity ring-down spectrometer was built up using a CW tunable Ti: sapphire laser. The experiments show that not only the spectral resolution is up to the 10(-4) cm(-1) level, but the detecting sensitivity also exceeds 10(-10) cm(-1). With the measurements of the absorption spectroscopy of C2H2 near 12,696.4 cm(-1), the quantitative capability of the instrument was demonstrated. Through the spectroscopy of the samples mixed with trace C2H2 in N2 gas, the detection limit of C2H2 was determined to be 0.2 ppm.

CO2 in solid para-hydrogen: spectral splitting and the CO2···(o-H2)n clusters.

Complicated high-resolution spectral structures are often observed for molecules doped in solid molecular hydrogen. The structures can result from miscellaneous effects and are often interpreted differently in references. The spectrum of the ν(3) band of CO(2) in solid para-H(2) presents a model system which exhibits rich spectral structures. With the help of the potential energy simulation of the CO(2) molecule doped in para-hydrogen matrix, and extensive experiments with different CO(2) isotopologues and different ortho-hydrogen concentrations in the matrix, the spectral features observed in p-H(2) matrix are assigned to the CO(2)···(o-H(2))(n) clusters and also to energy level splitting that is due to different alignments of the doped CO(2) molecules in the matrix. The assignments are further supported by the dynamics analysis and also by the spectrum recorded with sample codoped with O(2) which serves as catalyst transferring o-H(2) to p-H(2) in the matrix at 4 K temperature. The observed spectral features of CO(2)/pH(2) can potentially be used as an alternative readout of the temperature and orthohydrogen concentration in the solid para-hydrogen.